Process for the production of aromatic bodies and gas from petroleum oils.



F. W. MANN & M. L. CHAPPELL. PROCESS run THE PRODUCTION OF AHOMATIC BODIES AND GAS FROM PETROLEUM OILS.

APPLICATION HLED FEB. 3. 1916.

v Patented Jan. 30, 1917.

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i To all whom may concern.-

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aromatic bodies, naphthenes, and other ring" Be it known that we, Fminnarox Wmmnt MANN and MAnvm Lm: OHAPPELL, citizens of the United States, residing at Berkele in the county of Alameda and State of ali fornia, have invented certain new and-useful Improvements in Processes for the Production of Aromatic Bodies and Gas from Pe .troleum-Oils, of which the following is a specification.

Our invention relates to the art of manufacturing aromatic bodies and gas from petroleum oils containing oils of the carbocyclic series, and is particularly applicable for the production ofbenzol, toluol, xylol and other.

aromatic bodies, which are used extensively in the manufacture of dyes, explosives and The carbocyclic series consists of compounds, all of which are converted, or partlyconverted into aromatic oils by th I I process,benzol, toluol, xylol, etc.

a Our invention consists in the dehydrogenation of-such petroleum oils, under pressure below atmospheric, at high temperatures, in

the presence of air and in the presence-also of a contact substance. In the best practice of our process, the essentials are: a

ressure of from 1 to 4 inches of mercury elow atmospheric pressure, that is,'734.6 to, 658.4 millimeters of mercury absolute pres-.

sure a temperature ranging from 600 to 750 rick, pumice-stone, etc., with thesoluble salts ofnickel or iron or copper or with mixtures of these soluble salts We prefer to use the nitrates of these metals for the impregnation of such porous materials, and if one metal alone is employed, we prefer, as,

we have before stated, to use nickel. I

Afterthe impregnation, the contact mass is heated to a temperature ranging from 500 to 600 degrees oentigrade, in the presence of a reducin 'agent, vsuch as the vapors ofv petroleum 0' 8, carbon 'monoxid, and water,

vapor, which are-formed by-the chemical acnitro-benzol.

sive to maintain,

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tionflof petroleum oils" and air, according to the general reaction C,,H,,,-|- (O, Inca,- (CO) .By the action of such reducing agents the nitrates of the metals are converted into their lower oxids, thus r y j We are aware that certain processes are not now well known for the partial conversion i of petroleum oils at atmospheric and above atmospheric pressure, into oils of low boiling 'POllltSWhiCh contain small percentages of benzol and toluol, but we have found that it 1s not commercially profitable to separate this benzol and toluol from the undesirable oils. Such oils can 1 ,be used only for solvents and as fuel in internal combustion engines. Further, some of the undesirable oils formed under atmospheric or above atmospheric pressure have similar boiling points to benzol and toluol, and can be nitrated, but explode when heated to the boiling point of In general, we employ a reduced atmospheric pressure as stated, to pre- *vent the formation of these undesirable compounds, which cannot be separated from benzol and toluol by fractional distillation, and which, when nitrated, form dangerous explosives. A reduced pressure of more than 4 inches ofmercury below atmospheric may be employed with equally as good results, but such reduced pressures are'more'expen- In the accompanying drawindto which reference is hereby made, the figurq'represents an apparatus in which the process may be carried out. i

1 is an oil morage tank.

2 is a'shell having heating means indicated by the furnaces 3. Within this shell are two retorts 4 and 5, which, as seen through the broken out portion, contain the catalytic mass indicated by 6.

Ifrom the storage tank 1 leads a pipe 7, wh ch, by a branch pipe 8, controlled by a' valve 9, communicates-with one end of the retort 4 andb another branch pipe controlled hy' a. va vs 11 communicates Withthe retort 5. In each oi the branches 8 and '10 is a look-box 12 through which the size of the oil-stream can be seen. I I

13 isan air pi e which leads from any suitable source of -air, said ipe commun eating by a branch 14, contro led by a valve .15, with the retor't 4, and by another branch 16, controlled by a valve 17, communicating with the retort 5.

23 is a yrometer to indicate atureintere'tortam V From the retort 4 issues a pipe24, having a valve 25, said pipe connecting with a pipe 26 leading to gas-holder 27 -From the retort 5 issues a pipe 28, havinga valve 29, said pipe connecting with the pipe 26 which leads to the gas-holder 27. The two pipes 24 and 28 are directly connected by a pipe 30 havinga'valve 31 and another valve 32, one'valve being at each side of a pipe 33 which connects the pi e 30 with the top of a tank 34. Fromt e top 'of said tank 34 leads a pipe 35 which is coiled in a condenser box 36, and, emerging therefrom, leads into the to of a rethe temperceiver 37. From the top of this receiver leads the suction pipe 38 of ,a compressor 39, the dischar e pipe 40 offwhich is coiled v 37 and 42 are connected-byla pipe 3| in a condenser I I from, leads into a recelver 42. The receiver's pipe 43.

tithe form of avapor spray or a certain regulated quantity 0 air,-

44 by a pipe 46,'and discharges by a pipe 47 into a: storage tank 48. The receiver 42 is connected with the as-holder 27 by a pipe 49. The arrow in icate the courses of the fluids.

Our process is carried out in this appara- 1 tus as follows -Petroleum oils coming from the stor etank 1 fiowthrough the pi 7 and the branc 8 into the retort 4. This ow may be effectedeither I gravitation or under I pump pressure, and t e oil may be introduced either. in liquid state, into-the retort, "or in s, and with I namely 500 to 800- cubic .feet for each togallons of oil introduced. This air is admitted through pipe 13 and branch 14 and is is regulated y means I-of valve 15. If the I petroleum oils in liquid form'are used, then the size of their stream can. be observed through the look-box 12. The' temperature inside the retorts is maintained at from 600 to 750 degrees centi rade. At 'the saine time they are kept un er a pressure; of from 1 to 4 inches of "mercury below the atmospheric pressure, that is, 734.6 to 658.4 millimeters of mercury absolute pressure. This pressure below the atmospheric is mainx 41, and emerging therer tank 34' is c nected byewiththe and run into -'the receiver 37. The

tained-by means of :the suction pipe 38 of the compressor 39. The catalytic 6- in 'the retort becomes coated with carbon;

after the oil has been passing through it for some time. It is necessary to clean the catalyzer at the end of each run'of fortyor This is accomeightl'y minutes duration. I plished by closing the valve!) in 'the branch neously the valve 11 in the branch pipelO eum oils to the retort'f5, along with aii regard to their admission to retort 4. At the same time the valve controlling the discharge pipe 24' from the retort 4 is opened, and the valve 31 in the connecting is closed. Then the supply of air The temperature in the retort is kept tween 600 and 750-de ing the oxidation 0 s centi ade'dur- .the car on. The

bon monoxid and. little carbon dioxid are formed. The gases pass through the pipe 24-, (the' valve 25 being open) and thepipe 26' intothe gas-holder. 27. 'At the end of II twenty minutes-the'catalytic-mass is. freed is a pump which draws from the-pipe ,from' its coating of carbon. The quantity "of air is then reduced to a point between 500 and 800 cubic feet, and petroleum oil, oil 'sprayror oil va or is again turned into the 'retort 4. In 1i e mannerthe operation of cleaning the catalyzer takes place in retort 5, at the proper time.

The passage of the petroleum oils through. the catalytic material, as described, pro-,

pipe 8 whereby the flow of petroleum oils 3 I to the retort 4 is interrupted. I Simulta I is ripened in order to start the flow oi pei tro ' introduced through pipe l 3and-bra'n ch 16, I

and regulated by valve 17 ,both oil and air being in the proportions as abovestated with,

bodies is condensed. From the tank 34, the

uncondensed aromatic bodies-and the gas pass through the condensing coil of pipe 35 where more of said bodies are. condensed,

permanent gas retains a portion of the light mas-1 maticoils, which are removed from the re- 7 it ceiver .37, by the compressor 39',

I and beifi I condensed in the coil of pipe 40, are collec in the receiver .42, .from wh1ch the permanent gas enters the gas-holder 27, through the pipe 49. The aromatic bodies thus produced and collected in the tank 34 and receivers 37 and 42 are pumped into the storage tank 48, by means of the pump 45 and its con 95 amountofair is so regulated that only car'- nections. Finally they, are treated and fractionated by well known methods.

1. The process of producing aromatic bodies and gas which consists in the dehydro nation of petroleum oils containing oils of t e carboc clic series, under a pressure below atmosp eric, at temperatures ranging between 600 and 750 de centigrade, in the presence of air. an of a contact substance.

2. The process of producing aromatic bodies and gaswhich consists in the dehydrogenation of petroleum oils containing oils of the carbocyclic series, under a pressure below atmospheric, at temperatures ranging between 600 and ,7 50 degrees centigrade, in the presence of a volume of air ranging from 500 to 800 cubic feet for each ,15 or 20 gallons of oil subjected to treatment, and also in the presence of a contact substance.

3. The process of producing aromatic bodies and gas which consists in the dehydrogenation of petroleum oils containing oils of the carbocyclic series, under a pres-- sure of from 1 to 4 inches of mercury below atmospheric pressure, at temperatures ranging between 600 and 750 degrees centigrade, in the presence of a volume of air ranging from 500 to 800 cubic feet for each or gallons of oil subjected to treatment, and also in the presence of a contact substance.

4. The process of producing aromatic bodies and gas which consists in the dehydrogenation of petroleum, oils, containing oils of the carbocyclic series, under a pressure below atmospheric, at temperatures ran in between 600 and 750 degrees centigra e, in the resence of air and of the lower oxid of nicke two subscribin 5. The process of producing aromatic bodies and gas whichconsists in the dehydrogenation of petroleum oils containing oils of the carbocyclic series, under a pres sure below atmospheric, at temperatures ranging between 600 and 750 degrees centigrade, in the presence of a volume of air ranging from 500 to 800 cubic feet for each 15 or 20 gallons of oilsubjected to treatment, and also in the presence of the lower okid of nickel.

6. The process of producing aromatic bodies and gas which consists in the dehydrogenation of petroleum oils containing oils of the carbocyclic series, undera pressure of from 1 to Q inches of mercury below atmospheric pressure, at temperatures ranging between 600 and 750 degrees centigrade,

in the presence of a volume of air ranging from 500 to 800 cubic feet for each 15 or 20 gallons of oil subjected to treatment, and also in the presence of the lower oxid of nickel.-

7. The process of producing aromatic bodies'and gas which consists in the dehydrogenation of petroleum oils containing oils of the carbocyclic series, under a pressure below atmospheric, at temperatures ranging between 600 and 750 degrees centi- 70. grade, n the presence of air and of the lower oxid of a metal adapted for dehydrogenation. and molecular re-arrangement as described. I

Intestimony whereof we have signed our 5 names to this specification in the presence of witnesses.

. FREDE IGK WILLIAM MANN.

MARVIN LEE CHAPPELL.

Witnesses: p

WM. F. BOOTH, D. B. RICHARDS. 

